|Número de publicación||US7316719 B2|
|Tipo de publicación||Concesión|
|Número de solicitud||US 10/236,430|
|Fecha de publicación||8 Ene 2008|
|Fecha de presentación||6 Sep 2002|
|Fecha de prioridad||6 Sep 2002|
|También publicado como||CA2434977A1, EP1396471A2, EP1396471A3, US7655056, US20040048115, US20080070071|
|Número de publicación||10236430, 236430, US 7316719 B2, US 7316719B2, US-B2-7316719, US7316719 B2, US7316719B2|
|Inventores||John A. Devos|
|Cesionario original||Hewlett-Packard Development Company, L.P.|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (14), Citada por (33), Clasificaciones (31), Eventos legales (7)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
Over the past century the demand for energy has grown exponentially. With the growing demand for energy, many different energy sources have been explored and developed. One of the primary sources for energy has been, and continues to be, the combustion of hydrocarbons. However, the combustion of hydrocarbons is usually incomplete combustion and releases non-combustibles that contribute to smog as well as other pollutants in varying amounts.
As a result of the pollutants created by the combustion of hydrocarbons, the desire for cleaner energy sources has increased in more recent years. With the increased interest in cleaner energy sources, fuel cells have become more popular and more sophisticated. Research and development on fuel cells has continued to the point where many speculate that fuel cells will soon compete with the gas turbine generating large amounts of electricity for cities, the internal combustion engine powering automobiles, and batteries that run a variety of small and large electronics.
Fuel cells conduct an electrochemical energy conversion of hydrogen and oxygen into electricity and heat. Fuel cells are similar to batteries, but they can be “recharged” while providing power.
Fuel cells provide a DC (direct current) voltage that may be used to power motors, lights, or any number of electrical appliances. There are several different types of fuel cells, each using a different chemistry. Fuel cells are usually classified by the type of electrolyte used. The fuel cell types are generally categorized into one of five groups: proton exchange membrane (PEM) fuel cells, alkaline fuel cells (AFC), phosphoric-acid fuel cells (PAFC), solid oxide fuel cells (SOFC), and molten carbonate fuel cells (MCFC).
PEM Fuel Cells
The PEM fuel cells are currently believed to be the most promising fuel cell technology, and use one of the simplest reactions of any fuel cell. Referring to
The anode (20) is the negative post of the fuel cell and conducts electrons that are freed from hydrogen molecules such that the electrons can be used in an external circuit (21). The anode (20) includes channels (28) etched therein to disperse the hydrogen gas as evenly as possible over the surface of the catalyst (26).
The cathode (22) is the positive post of the fuel cell, and has channels (30) etched therein to evenly distribute oxygen (usually air) to the surface of the catalyst (26). The cathode (22) also conducts the electrons back from the external circuit to the catalyst, where they can recombine with the hydrogen ions and oxygen to form water. Water is the only by-product of the PEM fuel cell.
The electrolyte (24) is the proton exchange membrane (PEM) (24). The PEM is a specially treated porous material that conducts only positively charged ions. The PEM (24) prevents the passage of electrons.
The catalyst (26) is typically a platinum powder thinly coated onto carbon paper or cloth. The catalyst (26) is usually rough and porous so as to maximize the surface area of the platinum that can be exposed to the hydrogen or oxygen. The catalyst (26) facilitates the reaction of oxygen and hydrogen.
In a working fuel cell, the PEM (24) is sandwiched between the anode (20) and the cathode (22). The operation of the fuel cell can be described generally as follows. Pressurized hydrogen gas (H2) enters the fuel cell on the anode (20) side. When an H2 molecule comes into contact with the platinum on the catalyst (26), it splits into two H+ ions and two electrons (e−). The electrons are conducted through the anode (20), where they make their way through the external circuit (21) that may be providing power to do useful work (such as turning a motor or lighting a bulb (23)) and return to the cathode side of the fuel cell.
Meanwhile, on the cathode (22) side of the fuel cell, oxygen gas (O2) is being forced through the catalyst (26). In some PEM fuel cell systems the O2 source may be air. As O2 is forced through the catalyst (26), it forms two oxygen atoms, each having a strong negative charge. This negative charge attracts the two H+ ions through the PEM (24), where they combine with an oxygen atom and two of the electrons from the external circuit to form a water molecule (H2O).
The PEM fuel cell reaction just described produces only about 0.7 volts, therefore, to raise the voltage to a more useful level, many separate fuel cells are often combined to form a fuel cell stack.
PEM fuel cells typically operate at fairly low temperatures (about 80° C./176° F.), which allows them to warm up quickly and to be housed in inexpensive containment structures because they do not need any special materials capable of withstanding the high temperatures normally associated with electricity production.
Hydrogen Generation for Fuel Cells
As discussed above, each of the fuel cells described uses oxygen and hydrogen to produce electricity. The oxygen required for a fuel cell is usually supplied by the air. In fact, for the PEM fuel cell, ordinary air at ambient conditions is pumped into the cathode. However, hydrogen is not as readily available as oxygen.
Hydrogen is difficult to generate, store and distribute. One common method for producing hydrogen for fuel cells is the use of a reformer. A reformer uses hydrocarbons or alcohol fuels to produce hydrogen, which is then fed to the fuel cell. Unfortunately, reformers are problematic. If the hydrocarbon fuel is gasoline or some of the other common hydrocarbons, then SOx, NOx and other undesirable products are created. Sulfur, in particular, must be removed or it can damage the electrode catalyst. Reformers usually operate at high temperatures as well, which consumes much of the energy of the feedstock material.
Hydrogen may also be created by low temperature chemical reactions utilizing a fuel source in the presence of a catalyst. However, many problems are associated with low temperature chemical reactions for producing hydrogen. One of the primary problems is the requirement for pumps to move the chemical mixture into a reaction chamber filled with a catalytic agent. The use of a pump consumes at least some of the power that the fuel cell is generating (called parasitic power). If the power consumed by the pump becomes too high, the operation of the fuel cell to produce electricity becomes uneconomical.
Further, the chemical mixture provided to the reaction chamber must be accurately metered to facilitate a chemical reaction that will efficiently generate electric power. Accurate metering equipment adds expense, complexity, and sensitivity to the pumping system and increases the parasitic power consumption. Typical fuel cell systems are also usually orientation-specific, meaning that metering of the chemical mixture can only be done when the fuel cell system is in certain orientations. Orientation-specific fuel cell systems limit their usefulness for portable consumer electronics and other devices that may be used in multiple and changing orientations.
In addition, another challenge to using fuel cells in portable consumer products such as digital cameras and laptop computers is providing a hydrogen fuel source that is safe and energy-dense. While there have been fuel cell systems used to generate electricity (such as systems that use the PEM fuel cell described above), they are typically not small or dense enough to be used in most portable consumer products.
In one of many possible embodiments, the present specification provides a hydrogen generating apparatus including a chemical reaction chamber, a chemical solution reservoir, an unpowered pressure-producing member for moving a chemical solution from the chemical solution reservoir to the chemical reaction chamber, and a distributed catalyst bed about the chemical reaction chamber.
The foregoing and other features and aspects of the disclosed subject matter will become further apparent upon reading the following detailed description and upon reference to the drawings in which:
PIG. 3 is a diagrammatical view of hydrogen generator according to one embodiment of the principles disclosed herein.
In the drawings, identical reference numbers indicate similar, but not necessarily identical, elements. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Illustrative embodiments of the principles disclosed herein are described below. As will be appreciated by those skilled in the art, the subject matter of Ibis specification can be implemented in a wide variety of chemical reactions especially those for producing hydrogen for fuel cells. The fuel cell applications include, but are not limited to, PEM fuel cells, AYCs, PAFCs, SOECs, and MCFCs.
Turning now to the figures, and in particular to HG. 2, an overview of an electronic device (39) using a fuel cell power system is shown according to one embodiment. According to the embodiment of
The fuel cell (40) may provide power via an external circuit (48) to an electrical load (50). An electrical load may include any electrically operated device including, but not limited to, a digital camera, a laptop computer, and other portable electronics. The external circuit (48) may also be connected to an optional voltage regulator/control circuit (51) and an electrical capacitor or battery (52) which are shown in electrical parallel with the fuel cell (40). The optional voltage regulator/control circuit (51) may include a feedback loop (53) for providing data to the hydrogen generating apparatus (42). The electrical capacitor or battery (52) may provide auxiliary power to the electrical load (50).
The hydrogen generating apparatus (42) provides hydrogen gas to the fuel cell (40) so as to drive an energy-producing chemical reaction within the fuel cell (40). The hydrogen generating apparatus (42) may take many different forms. Referring to
Arranged about the fresh solution bag (56) may be an unpowered pressure-producing member, for example, a light-weight spring (58), located adjacent to the fresh solution bag (56). The term “unpowered” signifies that the pressure-producing member does not consume electrical energy to operate, nor does it require power from a motor. The spring (58) may include one or more members biased toward the fresh solution bag (56) to increase the pressure of the hydrogen-bearing fuel contained inside the fresh solution bag (56). In the embodiment shown, a plate (57) may be disposed between the fresh solution bag (56) and the spring (58). The pressure of the spring (58) is exerted on the plate (57), which, in turn, presses in upon the fresh solution bag (56). However, in some embodiments the plate (57) is not used and the spring (58) and fresh solution bag (56) are in direct contact.
According to the arrangement of the
The spring (58) of the present embodiment is disposed inside the chemical reaction chamber (60) between a wall (69) of the chemical reaction chamber (60) and the plate (57). Accordingly, the spring (58) applies a force to the fresh solution bag (56) via the plate (57) and facilitates movement of the hydrogen-bearing fuel from the fresh solution bag (56), through a porous distributed catalyst bed (59), and into the chemical reaction chamber (60). The distributed catalyst bed (59) may be substantially surrounding the chemical reaction chamber (60). In the embodiment shown, the distributed catalyst bed (59) is arranged about the sides of the chemical reaction chamber (60), but other arrangements may also be suitable. The distributed catalyst bed (59) is porous and may be supported by a wire or polymer mesh. The distributed catalyst bed (59) may include, but is not limited to, a noble metal catalyst such as ruthenium, rhodium, or platinum. The distributed catalyst bed (59) may include other metals such as nickel. The plate (57), the spring (58) and any other components may also be coated with a catalyst to further facilitate the chemical reaction.
The chemical reaction chamber (60) may include a wide variety of materials according to the reactants used to produce the hydrogen gas. The chemical reaction chamber (60) may be flexible or rigid, although in the present embodiment the chemical reaction chamber (60) is rigid. According to the embodiment of
The gas collection chamber (63) includes one or more fluid communications paths, such as a port (65), for supplying hydrogen gas to, for example, a fuel cell. A relief valve (67) may optionally be included in the port (65) for protection against overpressure. Another valve (not shown) may optionally be included for opening and closing the port (65) as needed.
As noted above, the movement bf the hydrogen-bearing tel from the fresh solution bag (56) to the chemical reaction chamber (60) may be facilitated by a fluid communication path such as a tubing (64). According to the embodiment shown in
In addition, the flow of the hydrogen-bearing fuel from the fresh solution bag (56) to the chemical reaction chamber (60) may be controlled by a valve, such as a micro-valve (66). The micro-valve (66) may be arranged at any convenient location along the tubing (64) or other fluid communication path for controlling the flow from the fresh solution bag (56). The micro-valve (66) is available from a variety of commercial sources. The micro-valve (66) is preferably normally closed. The valve (66) is preferably controlled by sending a series of signal pulses to the valve (66). The valve (66) is opened by arrival of a pulse and kept open for the duration of the pulse. Consequently, the volume of fuel flowing through the valve (66) can be controlled in a variety of ways, e.g., by controlling the time between pulses (micro-valve (66) pulsing frequency), the pulse width (duration the micro-valve (66) is held open), and/or valve aperture size. Variable aperture size control indicates analog control of how far open or closed the micro-valve is. The micro-valve (66) may thus enable precise control of the flow of the hydrogen-bearing fuel into the chemical reaction chamber (60). Alternatively, the micro-valve (66) may be mechanically operated by hand or by other mechanical apparatus. When hydrogen gas is needed, the micro-valve (66) is opened to allow the hydrogen-bearing fuel, pressurized by the spring (58), to flow into the reaction chamber (60). An optional relief and/or check valve (68) may also be included. In the embodiment shown, the relief and/or check valve (68) is located upstream of the micro-valve (66), but this is not necessarily so. Relief and/or check valves, such as the one shown, may be inserted at any point along the tubing (64). The relief and/or check valves (68) are commercially available from a number of different sources.
Operation of the hydrogen cartridge (54) may be described as follows. A hydrogen-bearing tel source, such as sodium borohydride is inserted into the fresh solution bag (56). In some embodiments, the fresh solution bag (56) may be inserted separately against the spring (58) after being filled. Alternatively, the fresh solution bag (56) may be filled while in the arrangement shown in
In some embodiments, the reaction chamber (60) may be supplied initially with water to fill any voids in the reaction chamber (60) and maximize volume utilization. And, because sodium borohydride mixes well with water, the concentration of the sodium borohydride in the fresh solution bag (56) may be slightly higher than would otherwise be used.
Prior hydrogen generating apparatus have required pumps of one kind or another to move the supply of hydrogen-bearing fuel from a reservoir to a reaction chamber. As indicated above, pumps add significantly to the parasitic losses of a fuel cell apparatus and occupy space, limiting the energy density available for the fuel cell apparatus. Advantageously, the principles disclosed herein decrease parasitic loss and reduces space requirement mechanical pressure source to facilitate movement of the hydrogen-bearing fuel from a reservoir to a reaction chamber.
According to the embodiment of
It will be appreciated by those of skill in the art having the benefit of this disclosure that the embodiments described advantageously provide for metering of a hydrogen-bearing fuel source to a chemical reaction chamber in an orientation-independent manner. That is, the hydrogen generating apparatus (42, 54.) may be operable in any orientation because the pressure-producing members provide a pressure differential between the fresh solution bag (56) and the reaction chamber (60) in any orientation. This may be especially important for fuel cell applications in portable electronics, which are often moved and reoriented in many different ways. In addition, some embodiments may use only a single control valve (66), reducing the occurrence of failures present in prior hydrogen generating systems that require pumps and multiple control valves.
Each of the embodiments described above preferably include a control valve to meter the transfer of a hydrogen-bearing fuel, such as sodium borohydride, from a chemical reservoir to a reaction chamber. Control of the hydrogen generation is facilitated by the control valve, such as the micro-valve (66) described above. Referring next to
The preceding description has been presented only to illustrate and describe the principles disclosed herein. It is not intended to be exhaustive or to limit the invention to any precise form disclosed. Many modifications and variations are possible in light of the above teaching. The preceding description is intended to enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US3594232 *||12 Jul 1968||20 Jul 1971||Varta Ag||Device for the automatic adjustment of the supply of liquids|
|US5635039||23 Nov 1994||3 Jun 1997||Lynntech, Inc.||Membrane with internal passages to permit fluid flow and an electrochemical cell containing the same|
|US5928409 *||12 Nov 1997||27 Jul 1999||New Jersey Institute Of Technology||Method and apparatus for gas removal by cyclic flow swing membrane permeation|
|US6024935||21 Mar 1997||15 Feb 2000||Blacklight Power, Inc.||Lower-energy hydrogen methods and structures|
|US6300000||18 Jun 1999||9 Oct 2001||Gore Enterprise Holdings||Fuel cell membrane electrode assemblies with improved power outputs and poison resistance|
|US6322917 *||27 Sep 1999||27 Nov 2001||Plug Power L.L.C.||Diagnostic method and control of preferential oxidation of carbon monoxide|
|US6383671||8 Sep 1999||7 May 2002||Lynntech, Inc.||Gas humidification device for operation testing and evaluation of fuel cells|
|US20030009942||11 Jul 2001||16 Ene 2003||Millennium Cell Inc.||Differential pressure-driven borohydride based generator|
|US20030235724 *||21 Jun 2002||25 Dic 2003||Ord Jason S.||Hydrogen generating apparatus|
|DE1667346A1||13 Mar 1968||9 Jun 1971||Varta Ag||Vorrichtung zur automatischen Nachfuehrung von Fluessigkeiten an ein Katalysatorbett|
|EP1170249A1||3 Jul 2001||9 Ene 2002||Toyota Jidosha Kabushiki Kaisha||Fuel gas generation system and generation method thereof|
|WO2001051410A1||5 Ene 2001||19 Jul 2001||Millennium Cell, Llc||System for hydrogen generation|
|WO2001074710A1||30 Mar 2001||11 Oct 2001||Manhattan Scientifics, Inc.||Portable chemical hydrogen hydride system|
|WO2002030810A1||11 Oct 2001||18 Abr 2002||Manhattan Scientifics, Inc.||Hydrogen source for operating a fuel cell and fuel cell provided within said source|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US8062797||6 May 2005||22 Nov 2011||Ardica Technologies, Inc.||Articles of clothing and personal gear with on-demand power supply for electrical devices|
|US8100993||13 Jul 2009||24 Ene 2012||Ardica Technologies, Inc.||Hydrogen generator|
|US8109286 *||10 Ago 2007||7 Feb 2012||Hitachi, Ltd.||Fuel tank including movable or deformable fuel chamber and waste chamber|
|US8172912||15 Nov 2004||8 May 2012||Encite, Llc||Self-regulating gas generator and method|
|US8187758||11 Ago 2005||29 May 2012||Ardica Technologies Inc.||Fuel cell apparatus with a split pump|
|US8192890||29 Ene 2009||5 Jun 2012||Ardica Technologies, Inc.||Fuel cell air exchange apparatus|
|US8500830 *||31 Ago 2010||6 Ago 2013||Young Green Energy Co.||Hydrogen generating apparatus and fuel cell using the same|
|US8741004||9 Jul 2010||3 Jun 2014||Intelligent Energy Limited||Cartridge for controlled production of hydrogen|
|US8764858||7 Feb 2011||1 Jul 2014||Intelligent Energy Inc.||Hydrogen gas generating apparatus with expandable reaction chamber|
|US8795926||31 Oct 2011||5 Ago 2014||Intelligent Energy Limited||Pump assembly for a fuel cell system|
|US8808410||29 Oct 2010||19 Ago 2014||Intelligent Energy Limited||Hydrogen generator and product conditioning method|
|US8940458||20 Oct 2010||27 Ene 2015||Intelligent Energy Limited||Fuel supply for a fuel cell|
|US9034531||26 Ago 2009||19 May 2015||Ardica Technologies, Inc.||Controller for fuel cell operation|
|US9169976||21 Nov 2012||27 Oct 2015||Ardica Technologies, Inc.||Method of manufacture of a metal hydride fuel supply|
|US9403679||11 Jul 2014||2 Ago 2016||Intelligent Energy Limited||Hydrogen generator and product conditioning method|
|US9409772||22 Abr 2014||9 Ago 2016||Intelligent Energy Limited||Cartridge for controlled production of hydrogen|
|US9515336||13 Ago 2015||6 Dic 2016||Intelligent Energy Limited||Diaphragm pump for a fuel cell system|
|US9522371||7 May 2012||20 Dic 2016||Encite Llc||Self-regulating gas generator and method|
|US9705145||15 Abr 2015||11 Jul 2017||Intelligent Energy Inc.||Hydrogen generator|
|US20050158595 *||15 Nov 2004||21 Jul 2005||Integrated Fuel Cell Technologies, Inc.||Self-regulating gas generator and method|
|US20050255349 *||6 May 2005||17 Nov 2005||Fisher Tobin J||Articles of clothing and personal gear with on-demand power supply for electrical devices|
|US20070011251 *||8 Dic 2005||11 Ene 2007||Mcnamara Kevin W||Fuel cartridge for fuel cell power systems and methods for power generation|
|US20070037034 *||11 Ago 2005||15 Feb 2007||Ardica Technologies||Fluid pump and connector assembly|
|US20070264190 *||9 May 2006||15 Nov 2007||Qinglin Zhang||Fixed-bed reactors and catalytic processes|
|US20080052994 *||10 Ago 2007||6 Mar 2008||Masafumi Nojima||Fuel tank|
|US20090269634 *||29 Ene 2009||29 Oct 2009||Tibor Fabian||System for purging non-fuel material from fuel cell anodes|
|US20090274595 *||13 Jul 2009||5 Nov 2009||Ardica Technologies, Inc.||Hydrogen generator|
|US20090305112 *||29 Ene 2009||10 Dic 2009||Fisher Tobin J||Fuel cell air exchange apparatus|
|US20100053852 *||2 Sep 2008||4 Mar 2010||Cheng Uei Precision Industry Co., Ltd.||Display Device|
|US20110020215 *||23 Jul 2009||27 Ene 2011||Ryu Wonhyoung||Chemical hydride formulation and system design for controlled generation of hydrogen|
|US20110053016 *||25 Ago 2010||3 Mar 2011||Daniel Braithwaite||Method for Manufacturing and Distributing Hydrogen Storage Compositions|
|US20110189558 *||31 Ago 2010||4 Ago 2011||Young Green Energy Co.||Hydrogen generating apparatus and fuel cell using the same|
|US20110194992 *||7 Feb 2011||11 Ago 2011||Eveready Battery Company, Inc.||Fuel Cell Cartridge|
|Clasificación de EE.UU.||48/197.00R, 422/129, 423/657, 429/416, 429/515, 429/410|
|Clasificación internacional||F17C11/00, H01M8/04, B01J7/02, B01J14/00, C01B3/36, B01J10/00, C01B3/06, C01B3/04, H01M8/06, C01B3/16|
|Clasificación cooperativa||Y02E60/364, B01J14/005, C01B3/065, F17C11/005, Y02E60/362, H01M8/04201, H01M8/04208, B01J7/02, Y02E60/321, H01M8/065|
|Clasificación europea||C01B3/06C, H01M8/06B4, B01J7/02, B01J14/00P, F17C11/00D|
|21 Feb 2003||AS||Assignment|
Owner name: HEWLETT-PACKARD COMPANY, COLORADO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DEVOS, JOHN A.;REEL/FRAME:013759/0857
Effective date: 20020814
|18 Jun 2003||AS||Assignment|
Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P., COLORAD
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:013776/0928
Effective date: 20030131
Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.,COLORADO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HEWLETT-PACKARD COMPANY;REEL/FRAME:013776/0928
Effective date: 20030131
|7 Abr 2009||CC||Certificate of correction|
|16 Jun 2011||AS||Assignment|
Owner name: EVEREADY BATTERY COMPANY, INC., MISSOURI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P.;HEWLETT-PACKARD COMPANY;REEL/FRAME:026463/0542
Effective date: 20101029
|8 Jul 2011||FPAY||Fee payment|
Year of fee payment: 4
|24 Ene 2014||AS||Assignment|
Owner name: INTELLIGENT ENERGY LIMITED, UNITED KINGDOM
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EVEREADY BATTERY COMPANY, INC.;REEL/FRAME:032124/0514
Effective date: 20131219
|8 Jul 2015||FPAY||Fee payment|
Year of fee payment: 8